CN116365062A - Lithium phosphide-based composite material and preparation method and application thereof - Google Patents
Lithium phosphide-based composite material and preparation method and application thereof Download PDFInfo
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- CN116365062A CN116365062A CN202310142012.7A CN202310142012A CN116365062A CN 116365062 A CN116365062 A CN 116365062A CN 202310142012 A CN202310142012 A CN 202310142012A CN 116365062 A CN116365062 A CN 116365062A
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- phosphide
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 142
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 29
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000001502 supplementing effect Effects 0.000 claims abstract description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 26
- 229910001416 lithium ion Inorganic materials 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 229910021389 graphene Inorganic materials 0.000 claims description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 11
- 239000007774 positive electrode material Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- 238000000498 ball milling Methods 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 239000002210 silicon-based material Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 239000013589 supplement Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000009469 supplementation Effects 0.000 description 2
- 239000011366 tin-based material Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000005184 irreversible process Methods 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5805—Phosphides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a lithium phosphide-based composite material, a preparation method and application thereof, and belongs to the technical field of secondary battery materials. The lithium phosphide-based composite material provided by the invention comprises fluorinated graphene and lithium phosphide dispersed on the surface and between layers of the fluorinated graphene. The lithium phosphide-based composite material provided by the invention can effectively improve the conductivity of lithium phosphide serving as a lithium supplementing material and reduce the sensitivity to water. The invention also provides a preparation method and application of the lithium phosphide-based composite material.
Description
Technical Field
The invention relates to the technical field of secondary battery materials, in particular to a lithium phosphide-based composite material and a preparation method and application thereof.
Background
The energy density of lithium ion batteries currently commercialized is approaching its theoretical limit. In order to further increase the energy density of lithium ion batteries, the development of novel electrode materials with high specific capacities is extremely important. When the negative electrode contains a part of high-capacity silicon-based materials or tin-based materials such as silicon, silicon carbon, silicon oxide, etc., active lithium in the positive electrode is further consumed to satisfy the growth of the negative electrode surface SEI film (solid electrolyte interphase) and a part of irreversible alloying reaction, eventually resulting in loss of active lithium in the full cell and a significant decrease in coulombic efficiency for the first time (the first few weeks).
In order to overcome the above drawbacks, researchers are struggling to develop lithium supplementing materials to supplement active lithium consumed in the SEI film generation process. Lithium phosphide (Li) 3 P) is considered to be an excellent lithium supplementing material because of its extremely high specific capacity (1550 mAh/g). However, its use for lithium supplementation is still limited in several respects. Firstly, the difficulty of preparing lithium phosphide with higher purity is higher at present. The lithium phosphide is an electronic insulator, and the room temperature lithium ion conductivity is very low<10 -8 S·cm -1 ) And is unfavorable for the rapid transmission of lithium ions. Thirdly, lithium phosphide is extremely unstable in air and is easy to react with water to generate lithium hydroxide and extremely toxic phosphine, so that further optimization and application of the lithium phosphide material are extremely difficult.
Therefore, a method for improving the performance of the lithium phosphide material is also needed to promote the application of the lithium phosphide material in the field of lithium supplementation.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides a lithium phosphide-based composite material which can effectively improve the conductivity of lithium phosphide serving as a lithium supplementing material and reduce the sensitivity to water.
The invention also provides a preparation method of the lithium supplementing material.
The invention also provides application of the lithium supplementing material.
According to an embodiment of the first aspect of the present invention, a lithium phosphide-based composite material is provided, the lithium phosphide-based composite material comprising graphene fluoride and lithium phosphide dispersed on the surface and between layers of the graphene fluoride.
The lithium phosphide-based composite material provided by the embodiment of the invention has at least the following beneficial effects:
(1) The lithium phosphide-based composite material provided by the invention comprises the fluorinated graphene, so that the lithium phosphide-based composite material has the electronic conductivity of the fluorinated graphene, and has higher electronic conductivity when being used as a lithium supplementing agent of a secondary battery.
(2) In the lithium phosphide-based composite material provided by the invention, lithium phosphide is dispersed between the layers of the fluorinated graphene, so that the fluorinated graphene is equivalent to isolating the lithium phosphide from the external environment, the chemical stability of the lithium phosphide is improved, the air sensitivity of the lithium phosphide is solved to a certain extent, and the cycle performance and the stability of a lithium battery can be obviously improved when the lithium phosphide-based composite material is used as a lithium supplementing agent of the lithium battery.
(3) The rich C-F bond of the fluorinated graphene and the two-dimensional nano structure thereof are beneficial to Li + Compared with pure lithium phosphide, the lithium phosphide-based composite material provided by the invention also remarkably improves Li + The conductivity finally improves the comprehensive electrochemical performance of the lithium phosphide-based composite material when the lithium phosphide-based composite material is used as a lithium supplementing agent.
(4) The inter-bonding structure of the fluorinated graphene and the lithium phosphide is not a rigid structure, and the interlayer of the fluorinated graphene cannot be completely filled with the lithium phosphide, so that when the fluorinated graphene is used as a lithium supplementing agent of a lithium ion battery, the lithium phosphide-based composite material can also accommodate volume change in the charging and discharging processes of part of the lithium ion battery, and further the comprehensive electrochemical performance of the obtained lithium ion battery is improved.
According to some embodiments of the invention, the mass ratio of the fluorinated graphene to the lithium phosphide is 1:0.1-9. For example, it may be 1:1, 6:1 or 9:1.
According to some embodiments of the invention, the fluorinated graphene has a thickness of 50-150nm.
According to some embodiments of the invention, the ionic conductivity of the lithium phosphide-based composite material is greater than or equal to 0.7X10 -2 S·cm -1 。
According to some embodiments of the invention, the electron conductivity of the lithium phosphide-based composite material is not less than 1.09×10 -2 S·cm -1 。
According to an embodiment of the second aspect of the present invention, a preparation method of the above lithium phosphide-based composite material is provided, specifically including mechanically grinding the lithium phosphide and the graphene fluoride.
The preparation method adopts all the technical schemes of the lithium phosphide-based composite material of the embodiment, so that the preparation method has at least all the beneficial effects brought by the technical schemes of the embodiment.
In addition, the lithium phosphide and the fluorinated graphene are compounded through simple mechanical grinding, and the preparation method is simple and easy to realize.
According to some embodiments of the invention, the lithium phosphide is prepared by mixing an organic solution of metallic lithium with red phosphorus.
According to some embodiments of the invention, the preparation of lithium phosphide is performed in an air-insulated environment, for example in a glove box filled with nitrogen or argon.
According to some embodiments of the invention, the method of preparing the organic solution comprises adding the metallic lithium to an organic solvent and stirring;
and (3) stirring the organic solution for 0.5-2 h.
According to some embodiments of the invention, the mass percentage of the metallic lithium in the organic solution is 10-60%. For example, it may be about 10%, 30% or 40%.
According to some embodiments of the invention, the organic solvent includes at least one of a mixture of benzene and tetrahydrofuran, a mixture of naphthalene and tetrahydrofuran, a mixture of biphenyl and tetrahydrofuran, a mixture of terphenyl and tetrahydrofuran, a liquid ammonia solution (CAS: 7664-41-7), a methylamine solution (CAS: 74-89-5), a dimethylamine solution (CAS: 124-40-3), an ethylamine solution (CAS: 75-04-7), and an ethylenediamine solution (CAS: 107-15-3).
According to some embodiments of the invention, when tetrahydrofuran is included in the organic solvent, the mass ratio of the remaining organic solvent to tetrahydrofuran is 0.5 to 5:1. For example, a mixture of benzene and tetrahydrofuran, the mass ratio of benzene to tetrahydrofuran is 0.5 to 5:1. For example, it may be about 3:1.
According to some embodiments of the invention, the red phosphorus comprises a pretreatment prior to use.
The pretreatment includes removing oxides from the red phosphorus surface with sodium hydroxide. Specifically, red phosphorus and aqueous sodium hydroxide solution are mixed at a temperature of 60 to 100 ℃. For example, it may be about 80 ℃.
According to some embodiments of the invention, the mass ratio of metallic lithium to red phosphorus is 1:0.1-9, for example, may be about 9:1 or 3:1 in particular.
According to some embodiments of the invention, the mixing reaction comprises stirring and standing performed sequentially. Wherein, stirring is used for improving mass transfer speed and promoting the full progress of the mixing reaction; the standing is to promote the sedimentation of the generated lithium phosphide.
According to some embodiments of the invention, the duration of stirring in the mixing reaction is 1-3 hours. For example, it may be about 2 hours.
According to some embodiments of the invention, the length of time of rest in the mixing reaction is 12-24 hours. For example, it may be about 12 hours.
According to some embodiments of the invention, the temperature of the mixing reaction is 40-100 ℃. For example, may be about 60 ℃.
According to some embodiments of the invention, the method further comprises solid-liquid separation after the mixing reaction, and drying the obtained solid product.
According to some embodiments of the invention, a method of preparing lithium phosphide comprises the steps of:
s1a, pretreating the red phosphorus by using the sodium hydroxide;
dissolving the metallic lithium in the organic solvent to form the organic solution;
s1b, mixing the red phosphorus obtained in the step S1a with the organic solution for reaction;
s1c, carrying out solid-liquid separation on the system obtained in the step S1b, and drying the obtained solid product to obtain the lithium phosphide;
the lithium phosphide is prepared in an air-insulated environment.
The lithium phosphide prepared by the preparation method has higher purity.
According to some embodiments of the invention, the preparing step of the fluorinated graphene comprises subjecting a mixture of graphene oxide and hydrofluoric acid to a hydrothermal reaction.
According to some embodiments of the invention, the graphene oxide is prepared from graphite as a raw material by Hummers.
According to some embodiments of the invention, the concentration of HF in the hydrofluoric acid in the hydrothermal reaction is 10-25mol/L. For example, it may be about 15mol/L.
According to some embodiments of the invention, in the hydrothermal reaction, the graphene oxide has a solid content of 80% -99%.
According to some embodiments of the invention, the temperature of the hydrothermal reaction is 120 ℃ to 180 ℃. For example, it may be about 150 ℃.
According to some embodiments of the invention, the hydrothermal reaction is for a period of 6-24 hours. For example, it may be about 12 hours or 16 hours.
According to some embodiments of the invention, the preparation of the fluorinated graphene further comprises solid-liquid separation after the hydrothermal reaction, and washing the obtained solid product with water to neutrality.
According to some embodiments of the invention, the method of mechanical milling comprises ball milling;
the ball-milled grinding beads are zirconia beads.
According to some embodiments of the invention, the rotational speed of the ball mill is 200-1000 rpm during the ball milling process; for example, it may be about 400rpm.
According to some embodiments of the invention, the ball milling time is 24-100 hours. For example, it may be about 36 hours or 72 hours.
According to some embodiments of the invention, the ball-milling process has a ball-to-material ratio of about 2:3.
The ball milling process is performed without temperature adjustment, i.e. at room temperature.
According to an embodiment of the third aspect of the invention, an application of the lithium phosphide-based composite material in a lithium ion battery anode lithium supplementing material is provided.
The application adopts all the technical schemes of the lithium phosphide-based composite material of the embodiment, so that the lithium phosphide-based composite material at least has all the beneficial effects brought by the technical schemes of the embodiment.
In addition, in the lithium phosphide-based composite material, the lithium phosphide crystal had 1547.61 mAh.g -1 The decomposition potential is 1V, which is far below the cutoff voltage of the positive electrode. The delithiation of lithium phosphide is an irreversible process, only involving the first charging process. Therefore, the lithium phosphide-based composite material can be applied to anode lithium supplement, but cannot be applied to cathode lithium supplement, and has the effect of improving the capacity of a lithium ion battery.
According to some embodiments of the invention, in the application, the negative electrode active material comprises a silicon-based material in a negative electrode matched with the positive electrode of the lithium ion battery.
According to an embodiment of the fourth aspect of the present invention, a lithium ion secondary battery is provided, the lithium ion secondary battery comprising a positive electrode, the preparation raw material of the positive electrode comprising a positive electrode active material and the lithium phosphide-based composite material.
The lithium ion secondary battery adopts all the technical schemes of the lithium phosphide-based composite material of the embodiment, so that the lithium ion secondary battery has at least all the beneficial effects brought by the technical schemes of the embodiment. Namely, the lithium ion secondary battery has the advantages of high initial coulombic efficiency, high capacity, good cycle performance and the like.
According to some embodiments of the invention, the lithium phosphide-based composite material comprises 0.2-1% by mass of the positive electrode active material. For example, it may be about 0.5%.
According to some embodiments of the invention, the positive electrode active material comprises at least one of a polyanionic positive electrode material and a layered positive electrode material;
the polyanionic material includes at least one of lithium iron phosphate, lithium manganese phosphate, and lithium manganese iron phosphate;
the layered positive electrode material comprises at least one of a lithium-rich material, a lithium cobaltate material, a lithium nickelate material, a lithium manganate material, a lithium nickelate manganate material, and a material formed by coating, doping and blending the materials on the basis of the materials.
According to some embodiments of the invention, the lithium ion secondary battery further comprises a negative electrode matched to the positive electrode;
the preparation raw materials of the negative electrode comprise a negative electrode active material;
the negative electrode active material includes at least one of a graphite-based material, a silicon-based material, and a tin-based material;
the silicon-based material includes a silicon oxygen material.
When the negative electrode active material comprises the silicon-based material, the lithium phosphide-based composite material exhibits more excellent performance as a positive electrode lithium-supplementing agent.
The term "about" as used herein, unless otherwise specified, means that the tolerance is within + -2%, for example, about 100 is actually 100 + -2%. Times.100.
Unless otherwise specified, the term "between … …" in the present invention includes the present number, for example "between 2 and 3" includes the end values of 2 and 3.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is a scanning electron microscope image of a lithium phosphide-based composite material obtained in example 1 of the present invention.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
Example 1
The embodiment prepares the lithium phosphide-based composite material, which comprises the following specific steps:
preparation of Li in a glove box in Ar atmosphere 3 P：
Mixing red phosphorus and sodium hydroxide aqueous solution at 80 ℃ for pretreatment to remove surface oxides; the concentration and mixing time of the aqueous sodium hydroxide solution in this step are not limited as long as the oxide on the surface of red phosphorus can be removed.
Dissolving metallic lithium in an organic solvent, and stirring for 0.5h to obtain an organic solution; the mass percentage of the metal lithium is 10%; wherein the organic solvent is prepared by mixing benzene and tetrahydrofuran according to a mass ratio of 3:1.
Controlling the temperature to 60 ℃, adding pretreated red phosphorus into the organic solution, stirring for 1h, standing for 12h, centrifuging, and drying the obtained product to obtain Li 3 P is as follows; the mass ratio of the metal lithium to the red phosphorus is 1:9;
preparation of Fluorinated Graphene (FG):
graphene oxide is prepared by using graphite through Hummers, hydrofluoric acid (the concentration is 15 mol/L) and graphene oxide dispersion liquid are added into a reaction kettle, then hydrothermal reaction is carried out at the temperature of 150 ℃ for 16 hours (the solid content of the graphene oxide in a reaction system is 80%), and deionized water is used for washing until the pH value is neutral after the reaction.
Preparation of lithium phosphide-based composite Material (Li) 3 P@fg): fluorine is added toChemical graphene powder and Li 3 P is placed in a zirconia ball milling tank, and the mass ratio is 1:9; mechanically ball-milling to obtain Li 3 P@FG composite material; wherein the rotation speed of the ball mill is 400rpm, the grinding balls are zirconia balls, the ball-to-material ratio is 2:3, and the ball milling time is 72 hours.
Preparation of graphene fluoride and preparation of Li in this example 3 There is no sequence between the two steps P, as long as both are before preparing the lithium phosphide-based composite material;
in the preparation of Li 3 In the process of P, the pretreatment of red phosphorus and the configuration of organic solution are not in sequence.
The morphology test shows that the lithium phosphide-based composite material obtained in the embodiment is a composite of a granular material and a film-like material, wherein the granular material is filled between layers of the film material. It was thus demonstrated that lithium phosphide was located between and on the surface of the graphene fluoride, which was about 50nm thick. The specific test results are shown in fig. 1.
The ionic conductivity of the lithium phosphide-based composite material obtained in this example was 0.7X10 -2 S·cm -1 The electronic conductivity is more than or equal to 1.09 multiplied by 10 -2 S·cm -1 。
Example 2
The lithium phosphide-based composite material is prepared in the embodiment, and the specific difference from the embodiment 1 is that:
(1) Preparation of Li 3 In the P process:
the mass percentage of the metal lithium in the organic solution is 30%;
the mass ratio of the metal lithium to the red phosphorus is 3:1;
(2) In the process of preparing the lithium phosphide-based composite material:
fluorinated graphene powder and Li 3 The mass ratio of P is 1:1.
Example 3
The lithium phosphide-based composite material is prepared in the embodiment, and the specific difference from the embodiment 1 is that:
(1) Preparation of Li 3 In the P process:
stirring for 1h to obtain an organic solution, wherein the mass percentage of the metal lithium is 40%;
stirring for 2h and standing for 24h in the mixing reaction process of the organic solution and the red phosphorus;
the mass ratio of the metal lithium to the red phosphorus is 9:1;
(2) In the process of preparing the lithium phosphide-based composite material:
fluorinated graphene powder and Li 3 The mass ratio of P is 6:1.
comparative example 1
This comparative example produced a lithium phosphide-based composite material, which was different from example 1 in particular in that:
comprises only the preparation of Li 3 P step, i.e. Li 3 P is used as a lithium phosphide-based composite material;
and Li is prepared 3 In the step P, the mass ratio of the metal lithium to the red phosphorus is 3:1.
Comparative example 2
This comparative example produced a lithium phosphide-based composite material, which was different from example 2 in particular in that:
(1) Preparation of Li 3 In the P process:
the mass percentage of the metal lithium in the organic solution is 30%;
(2) Excluding the step of preparing the fluorinated graphene;
(3) FG of example 1 was replaced with an equal amount of reduced graphene oxide in the preparation of lithium phosphide-based composite material.
The reduced graphene oxide of the present comparative example was obtained by reducing graphene oxide prepared by the Hummers method with a reducing agent (ascorbic acid). Wherein the mass ratio of the reducing agent to the graphene oxide is 1:1.
Test case
The test example uses the lithium phosphide-based composite materials obtained in examples 1-3 and comparative examples 1-2 as the performance of a positive electrode lithium supplementing agent, and specifically:
the negative electrode active material is a mixture of artificial graphite (fir science and technology Co., ltd.) and a silicon oxide material (silica, yi Jin Xin energy science and technology Co., ltd.) in a mass ratio of 93:7;
the positive electrode active material is LiCoO 2 Lithium is supplemented to the positive electrodeThe dosage of the agent is 0.5% of the mass of the positive electrode active material;
the diaphragm adopts a JL 7 mu m oil-based diaphragm;
obtaining a bare cell by adopting a full-automatic winding mode; and (3) jacking the bare cell by using an aluminum plastic film outer package with a certain size, injecting a certain amount of electrolyte into the dried semi-packaged cell, and completing packaging. The cell electrolyte injection coefficient is 1.7, and the N/P value is 1.08.
And (3) continuing the working procedures of standing, formation, shaping, capacity division and the like of the battery to finish the preparation of the lithium ion soft package battery.
The prepared lithium ion soft-pack battery (specific embodiment of lithium phosphide-based composite material source is numbered) is cycled in a voltage range of 3.0-4.48V according to a charge-discharge multiplying power of 0.2C/0.5C at a temperature of 25+/-3 ℃, and the coulombic efficiency, the gram specific discharge capacity at the first week and the ratio of gram specific capacity at the first week to gram specific capacity at the first week (capacity retention rate at 700 weeks) are recorded. The specific test results are shown in table 1.
TABLE 1 Properties of lithium phosphide-based composite materials obtained in examples 1 to 3 and comparative examples 1 to 2 as Positive electrode lithium-supplementing agent
The results in table 1 show that when the lithium phosphide-based composite material provided by the invention is used as a positive electrode lithium supplementing agent, the first-week coulomb efficiency and gram specific capacity of the obtained lithium ion battery can be effectively improved.
However, if the lithium phosphide-based composite material does not include the fluorinated graphene (comparative example 1) or the fluorinated graphene is replaced with conventional reduced graphene oxide, the first-week coulombic efficiency and gram specific capacity of the resulting lithium ion battery may be significantly reduced. Therefore, the mutual coordination between the fluorinated graphene and the lithium phosphide can obviously promote the lithium supplementing effect of the lithium phosphide. In the lithium ion batteries corresponding to the embodiments 1-3, the cycle performance is better than that of the comparative examples 1-2, so that the lithium phosphide-based composite material provided by the invention has weaker air sensitivity, and the lithium phosphide-based composite material after the lithium supplementing effect is exerted, and the cycle performance of the lithium ion battery can be improved to a certain extent.
While the embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (10)
1. The lithium phosphide-based composite material is characterized by comprising fluorinated graphene and lithium phosphide dispersed on the surface and between layers of the fluorinated graphene.
2. The lithium phosphide-based composite material according to claim 1, wherein the mass ratio of the fluorinated graphene to the lithium phosphide is 1:0.1-9.
3. A method of preparing a lithium phosphide-based composite material as set forth in claim 1 or 2, characterized in that the method comprises mechanically grinding the lithium phosphide and graphene fluoride.
4. The method of claim 3, wherein the step of preparing the fluorinated graphene comprises subjecting a mixture of graphene oxide and hydrofluoric acid to a hydrothermal reaction.
5. A method of producing according to claim 3, characterized in that the method of producing lithium phosphide comprises mixing an organic solution of metallic lithium and red phosphorus for reaction.
6. The method according to claim 5, wherein the mass percentage of the metal lithium in the organic solution is 10 to 60%.
7. The method according to claim 5, wherein the mixing reaction comprises stirring and standing performed sequentially; preferably, the stirring time is 1-3 h; preferably, the standing time is 12-24 hours.
8. Use of the lithium phosphide-based composite material as set forth in claim 1 or 2 in a lithium ion battery positive electrode lithium supplementing material.
9. A lithium ion secondary battery, characterized in that the lithium ion secondary battery comprises a positive electrode, and the preparation raw material of the positive electrode comprises a positive electrode active material and the lithium phosphide-based composite material as set forth in claim 1 or 2.
10. The lithium ion secondary battery according to claim 9, wherein the lithium phosphide-based composite material accounts for 0.2 to 1% by mass of the positive electrode active material.
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